Controlling aqueous microorganisms with n-polyhalovinylthio carboxamides

ABSTRACT

WHERE R is an aliphatic hydrocarbon radical of one to 10 carbon atoms which has 0 to about 3 halogen substituents of atomic number 17 to 35, R&#39;&#39; is hydrogen or alkyl of one to four carbon atoms with the proviso that R and R&#39;&#39; may be joined to form a linear alkylene radical of three to five carbon atoms which is bound to the carbonyl and nitrogen to form a ring, X is halogen of atomic number 17 to 35 and a is 2 or 3. These carboxamides are fungicidal, algicidal and nematocidal.   N-polyhalovinylthiocarboxamides of the formula:

United States Patent [1 1 Brown Nov. 13, 1973 CONTROLLING AQUEOUS MICROORGANISMS WITH N-POLYHALOVINYLTHIO CARBOXAMIDES [75] Inventor: Melancthon S. Brown, Berkeley,

. Calif.

[73] Assignee: Chevron Research Company, San

Francisco, Calif.

[22] Filed: May 15, 1972 [21] Appl. No.: 253,642

Related U.S. Application Data [60] Division of Ser. No. 33,879, April 30, 1970, Pat. No. 3,679,673, which is a continuation-in-part of Ser. Nos. 810,368, March 25, 1969, abandoned, and Ser. No. 748,642, June 30, 1968, abandoned, said Ser. No. 810,368, Continuation-impart of Ser. No. 748,642, and Ser. No. 704,555, said Ser. No. 748,642, Continuation-in-part of Ser. No. 810,377.

[52] U.S. Cl 71/66, 7l/67, 71/88, 71/95 [51] Int. Cl ..A01n 9/12 [58] Field of Search ..71/66, 67, 98, 88, 71/94, 95; 162/161; 210/64 [5 6] References Cited UNITED STATES PATENTS 3,629,419 12/1971 Moon ..71/67 Kuhle et al 260/453 R Kohn 424/273 Primary Examiner-Glennon H. Hollrah Attorney-J. A. Buchanan, Jr. et al.

[5 7] ABSTRACT N-polyhalovinylthiocarboxamides of the formula:

7 Claims, No Drawings CROSS REFERENCE TO RELATED APPLICATIONS I This application is a division of application Ser. No. 33,879, filed Apr. 30, 1970, now US. Pat. No. 3,679,673, which application is a continuation-in-part of application Ser. No. 810,368, filed Mar. 25, 1969, now abandoned and application Ser. No. 748,642, filed June 30, 1968, now abandoned. Application Ser. No. 810,368 is a continuation-in-part of application Ser. No. 748,642 and application Ser. No. 704,555, filed Feb. 12, 1968, now abandoned. Application Ser. No. 748,642 is a continuation-in-part of application Ser. No. 704,555. Related application Ser. No. 810,377 was filed Mar. 25, 1969 now abandoned.

FIELD OF INVENTION This invention concerns N-polyhalovinylthiocarboxamides and their use as pesticides, especially as nematocides.

INVENTION DESCRIPTION The novel carboxamides of the present invention may be represented by the formula wherein R is an aliphatic hydrocarbon radical of one to 10 carbon atoms which has to 3 halogen substituents of atomic number 17 to 35, i.e., R is alkyl of one to carbon atoms, alkenyl of two to 10 carbon atoms, alkynyl of two to 10 carbon atoms, haloalkyl of one to 10 carbon atoms and one to three halogen atoms of atomic number 17 to 35, cycloalkyl of three to 10 carbon atoms, cycloalkyl of three to 10 carbon atoms, preferably cyclohexyl, substituted with one to three halogen atoms of atomic number l7.to 35, or cycloalkenyl of three to 10 carbon atoms; R" is hydrogen'or alkyl of one to four carbon atoms with the proviso that R and R may be joined to form a linear alkylene radical of three to five carbon atoms which is bound to the'carbonyl and nitrogen to form a ring; X is halogen of atomic number 17 to 35; and a is 2 or 3.

Preferably X is chlorine; a is 3; R is an aliphatic hydrocarbon radical of one to eight carbon atoms which is free of aliphatic unsaturation and has 0 to 3 halogen substituents, more preferably 0 to 2 chloro substituents, i.e., R is alkyl of one to eight carbon atoms,'haloalkyl of one to eight carbon atoms and one to three halogen atoms of atomic number l7to 35, more preferably one to two chlorine atoms, cycloalkyl of three to eight carbon atoms, or cycloalkyl of three to eight carbon atoms substituted with one to three halogen atoms of atomic number 17 to 35, more preferably one to two chlorine atoms; and R is hydrogen or alkyl of one to two carbon atoms.

The carboxamides in which R and R are joined to form a ring with the carbonyl and nitrogen may alternatively be represented by the formula trichlorovinylthio-3,3-dichloropropionamide,

wherein R is linear alkylene of three to five carbon atoms and X and a are as defined previously.

Representative polyhalovinyl groups which C X,,l-I may represent are trichlorovinyl, 1,2- dichlorovinyl, 2,2-dichlorovinyl, tribromovinyl, 2,2- dibromovinyl, 1,2-dibromovinyl, 2-bromo-2 chlorovinyl and the like. 4

Organic groups which R in formula (1) above may represent are alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl. Specific examples of such groups are methyl, ethyl, isopropyl, n-butyl, properyl, propynyl, sec.butyl, amyl, hexyl, octyl, decyl, 3-methylamyl, cyclobutyl, cyclohexyl, 'cyclooctyl and the like. Halosubstituted radicals which R may represent include chloroalkyl, bromoalkyl, chlorocycloalkyl and bromocycloalkyl. Specific examples of such halosubstituted radicals are chloromethyl, 2-chloroethyl, 3-chloropropyl, 4-chloroamyl, o-chlorohexyl, pchlorocyclohexyl, 2,6-dichlorocyclohexyl, 2,6- dibromocyclohexyl and p-bromocyclohexyl.

Alkyl radicals which R may represent include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl. Alkylene radicals which R and R taken together or R may represent are propylene, butylene and amylene.

Typical carboxamides represented by the above formulas and N-trichlorovinylthioacetamide, N-tribromovinylthioacetamide, N-l ,2- dichlorovinylthioacetamine, N-2-bromo-2- chlorovinylthioacetamide, N-methyl-N-l ,2- dibromovinylthioacetamine, N-ethyl-N-trichlorovinylthioacetamide, I N-isobutyl-N-2-bromo-2- chlorovinylthioacetamide, N-tribromovinylthiochloroacetamide N-ethyl-N- l -chloro-2-bromovinylthiobromoacetamide, N-l,2-dibromovinylthiopropionamide, N-2,2-dichlorovinylthiopropionamide, N-2 bromo-2-chlorovinylthiopropionamide, N-methyl-N- trichlorovinylthiopropionamide, N-isopropyl-N-1- chloro-2-bromovinylthiopropionamide, N-n-butyl-N- 1 ,2-dichlorovinylthiopropionamide, N

methyl-N-2,2 dichlorovinylthio-2,3-

dibromopropionamide, N-butyl-N-1-chloro-2- bromovinylthiochloropropionamide, N-l ,2- dichlorovinylthiobutyramide, N-l-chloro-2- bromovinylthiobutyramide, N-propyl-N-l,2- dibromovinylthiobutyramide, N-methyl-N-Z-bromo-Z- chlorovinylthiopentamide, N-trichlorovinylthio-3,4,5- trichloropentanamide, N-butyl-N-tribromovinylthiohexanamide, N-2-bromo-2-chlorovinylthio-5- bromohexamide, N-ethyl-N-trichlorovinylthioheptanamide, N-2 ,2-dichlorovinylthio-6 ,7- dichloroheptanamide, N-trichlorovinylthiooctanamide, N-propyl-N -2,2-dichlorovinylthio-3 ,5 ,7- tribromooctanamide, N-trichlorovinylthiodecanamide, N-methyl-N-l ,2-dibromovinylthio- 1 0- trichlorovinylthio-3-hexenamide, N-trichlorovinylthio- 3-decenamide, N-trichlorovinylthiopropiolamide, N-

trichlorovinylthio-3-butynamide, N-

trichlorovinylthiocyclooctanecarboxamide, N-propyl- N-tribromovinylthio-3,4-dichlorocyclohexanecarboxamide, N-trichlorovinylthio-4-bromocyclohexanecarboxamide, N-methyl-N-l-chloro-2-bromovinylthio-2- chlorocyclobutanecarboxamide, N- trichlorovinylthiocyclohexenecarboxamide, N-butyl- N-2-brom0-2-chlorovinylthiocyclohexenecarboxamide, N-trichlorovinylthiopyrrolidone, N- tribromovinylthiopyrrolidone, N-l -chloro-2- bromovinylthiopyrrolidone, N-trichlorovinylthiopiperidone, N-l,Z-dibromovinylthiopiperidone, N-2-bromo- 2-chlorovinylthiopiperidone, N-trichlorovinylthiocaprolactam, N-2,2-dichlorovinylthiocaprolactam and N-1-chloro-2-bromovinylthiocaprolactam.

The carboxamides of this invention may be prepared by reacting a sulfenyl halide with a primary or secondary carboxamide or a lactam. This reaction is illustrated by the following chemical equation:

where R, R, X and a are as previously defined. It is desirable to carry out this reaction in the presence of inert solvents such as dimethylsulfoxide, dimethylformamide, acetonitrile, dioxane and the like. The reaction temperature is, in general, not critical and will usually be in the range of about 20 to about 50C., preferably about to 20C. Likewise, the pressure is not critical and will usually be atmospheric or autogenous. It is desirable to use stoichiometric proportions of the reactants or a slight excess of the sulfenyl halide reactant.

In reactions wherein R is an organic group, it is necessary to have a mild, basic halogen halide acceptor present. At least stoichiometric amounts of acceptor should be used. Soluble tertiary amines such as pyridine and trialkylamines, e.g., triethylamine and tripropylamine are preferred. Acceptorswhich are strong enough to react with the sulfenyl halide reactant should be avoided.

Carboxamides of this invention may also be prepared by dehydrohalogenating corresponding polyhaloalkylthiocarboxamides. For instance, N-(tetrachloroethylthio) carboxamides may be dehydrochlorinated to produce N-trichlorovinylthiocarboxamides. This dehydrohalogenation will normally be carried out at low temperatures, usually about 0 to 40C.

and in the presence of solvents such as benzene, toluene, ether, methylene chloride, acetonitrile and chloroform. Mild dehydrohalogenating agents such as tertiary amines (trialkyl amines, pyridine, etc.) or alkali. metal carbonates will normally be employed. Triethylamine is a preferred agent.

EXAMPLES The following examples describe methods which may be used to prepare the carboxamides of this invention. These examples are not intended to limit the invention described herein. Percentages are by weight.

EXAMPLE 1 15 g. of acetamide and 100 ml. dimethylformamide were placed in a vessel cooled in an ice bath. 20 g. of freshly distilled trichlorovinylsulfenyl chloride was added slowly to th-is mixture. After this addition, the vessel was removed from the ice bath and allowed to stand for 1 hour at ambient temperature. 1 liter of ice water was then added to the vessel causing a precipitate to form. The vessels contents were then filtered and washed with water and hexane. The solid was then dissolved in methylene chloride and the solution was dried over MgSO,,. After drying, the methylene chloride was stripped off leaving 11 g. of N-trichlorovinylthioacetamide. This compound, a white solid, melted at 7982C. Its S and Cl analyses were:

Calculated Found EXAMPLE 2 Calculated Found S 12.55 12.52 Cl 55.6 53.3

The melting point of the compound was 85-95C.

Other carboxamides of this invention were prepared by the method described in Example 1. These carboxamides are listed in Table l.

TABLE I Element analyses, percent S Cl Melting point,

Compound Calculated Found Calculated Found C N-trichlorovinylthlochloroacetamide 12. 12. 52 55. 6 53.3 85-90 N-trichlorovlnyltblopropionamide 13. 13. 62 45. 4 45. 60 -83 N-trichlorovinylthiocyclohexanecarboxam 11. 06 11. 23 36. 8 36. 55 146-149 N-trlchlorovinylthio-n-butyramide 12. 87 12. 92 42. 8 42. 30 65-68 N-trichlorovlnylthio-n-bexauamido. 11. 57 11. 88 38. 42 38. 52 46-50 N-trlchlorovlnylthiolsobutyramide.--- 11. 8 12. 37 39. 3 41. 94 95-100 N-trichlorovlnylthiotrlmethylacetamide 12. 15 12. 22 40. 45 39. 125-128 N-trlchlor0vlnylthiocyclopropanecarboxamlde 12. 97 13. 12 43. 1 42. 70 88-91 N-methyl-N-trichlorovlnylthioacetamide 13. 62 13. 28 45. 3 44. 6 Oil N-methyl-N-trlchlorovlnylthiobutyramlde 12. 18 12.38 40. 5 40. 5 Oil N-trlchlorovlnylthlopyrrolidone 12. 96 13. 10 43. 1 41. 9 Oil N-tricl\10rovlnylthiocaprolactam 11. 64 11. 68 38. 7 38. 65 Oil N -2,2-dichlorovlnylthiopropionamide 16. 00 15. 72 35. 45 35. 18 83-85 N-2,2-dichlorovinylthiotr1methylacetamide 14. 01 13. 98 31. (m 30. 96-98 15. 10 14. 68 33. 50 32.70 07-102 N -2,2-dichlorovlnylthlopyrrolidone UTILITY by exposing them to a toxic amount of the carboxamide. Thus, these carboxamides willnormally be applied to nematode-infested soil at dosages in the range of 3 to 40 lbs. per acre. They may be applied as liquid for- 5 mulations by spraying or injection. The liquid formulations of these carboxamides may be solutions, dispersions, or emulsions. Typical solvents which may be used are aromatics such as xylene, toluene and benzene, ketones such. as eyclohexanone and the like. f 10 These liquid formulations will usually contain a wetting agent to facilitate the carboxamides penetration into the soil and generally enhance its effectiveness. They may also be applied as solid formulations containing carriers such as soil, sawdust, clay and the like. When lowing method. 5 used as a solid, these carboxamides will usually be A 0.38 ml. portion of a 3 percent acetone solution of plowed into the soil- Following their application to the the test compound was diluted with 1 1 acetohe The soil, the soil will be watered to disperse the carboxamresulting solution was homogenously mixed with cc. below ghouhd level of vermiculite. The treated vermiculite was then mixed carhoxamlde? of h f h are Parhcularly homogenously with 750 of Soil, dry weight basis, 20 ful for controlling microbiological organisms such as which was severely infested with free-living nematodes algae bacteha molds and occaslohahy aqhahc weeds (mixed culture of Meloidogyne javanica and Meloidowhich foul aqueous ihdhsh'ihl effluents ahd coohhg gyne incognita). This mixing gave a concentration of streams, suchas those occurring in the paper and food approximately 15 parts of the test compound per processing industries. They may also be used to control lion parts of soil. This treated soil was stored for 4 days Such orgamsms m other aqueous; bodies Such as lakes at 65-75F. it was then divided equally into 3 parts, h a h h pools and the wheh so h a each of which was put into a separate pot and kept for bloclfiai one or more of the carboxamldis another 3 days A 3 week old tomato Bonny Best) of this invention is added to the aqueous growth env seedling was then transplanted into each pot and incuronmegt of the thls dosage bated for 13 days under greenhouse conditions. After range etween.a out an In any given mthis period they were removed and the soil was washed t the ohnmum dosage depehd upon the a from their roots. The nematocidal effectiveness of the ucular orgamsm and aqueous body Involved For test compound was determined y observing each plant stance, when used to control algae, these carboxamides for Signs of nematode invasion (number of galls will usually be employed at concentrations of about 0.1

formed, stunting etc). to 10 ppm. In terms of pounds of carboxamide per acre The results of these tests, reported as the average of g zr g i g f zi Els :2: ig f gz to 5 .2 the 3 replicates on a 0 to 100 basis 0 indicating no p ese rboxam'd ma b d t effectiveness; 100 indicating complete effectiveness ca 1 es y e applie o h growth environments of such organisms as dispersible powders are reported in Table II.

40 or in solution with water-miscible solvents.

The N-polyhalovinylthiocarboxamides of this invention have exhibited biological activity against a variety of organisms, particularly fungi, algae and nematodes. Their activities against nematodes were unexpectedly better than those of the most closely related known carboxamides, the N-polyhaloalkylthiocarboxamides. Also, many of them were significantly better fungicides and algicides than the known carboxamides.

The nematocidal activities of the carboxamides 0 this invention and their superiority over corresponding N-polyhaloalkylthio compounds were illustrated by testing representative amides of this invention and representative N-polyhaloalkylthio compounds by the fol- TABLE II Representative carboxamides of this invention were Nematocidal activity. percent tested as algicides by the following method.

subshment An acetone solution-of equal parts of carboxamide Trichlorp- Trlchloro- 1.1.2.2-tetraand a surfactant was prepared. This solution was mixed Carboxamide moiety vinylthio methylthlo chloroethylthio with a nutrient broth in a quantity Sufficient to give a 100 42 concentration of 2 ppm. carboxamide. Four replicate HgC-C-NH v 150 ml. specimen cups were filled with this mixture. 0 96 15 Y 0 350-400 mg. of Euglena was added to'each specimen cup and the cups were then placed in an environment II E ClC-CNH- a chamber for incubation. The cups were observed perii 99 odically for algae growth. The algicidal effectiveness of Ha 2)rC-NH the carboxamide was determined based on a final obs3 servation of algae growth after 10 days.

The results of these tests, reported. as the average of mowmn-ii-rmthe 4 replicates on,a 0 to 100 basis 0 indicating no 0 100 effectiveness; 100 indicating complete effect veness HBCTCTNHT are reported in Table Ill.

81 TABLE III HiCCN(CHi)- Algicidal 56 60 Compound efiectiveness N-trichlorovinylthiochloroacetamlde.. 100 N-trichlorovinylthioacetamide 100 N-trichlorovinylthiopropionamide 100 O N-trichlorovinylthiocyclohexanecarboxam i N-trichlorovinylthiobutyramide 100 100 N-trlchlorovinyithioisobutyramlde 96 65 N-trichlorovinylthiotrimethylacetemide 100 I N-trichlorovinylthiocyclopropanecarboxamide 100 N-methyl-N-trichlorovinylthioacetamide 100 N-trichlor0vinylthiopyrroli done 100 w I e N -trichlorovinylthiocaprolactam 100 N-methyl-N-trichlorovinylbutyramlde. 100 As illustrated above, the carboxamides of this invench o 0 y w y a e nfl N-2.2-dichlo ovin lthio rrolldone tion may be used to control plant-parasitic nematodes y I V H Comparative algicidal testing indicated the carboxamides of this invention were more effective than corresponding N-polyhaloalkylthiocarboxamides.

Carboxamides of this invention were also used to control fungi such as Pythium ultimum, Rhizoctonia solani, Fusarium oxysporum, f. phaseoli, Helminthos- -porium sativum, Verticillium albo-atrurn, Monilinia fructicola and Altemaria solani and bacteria such as Erwinia caratovara and Pseudomonas syringae. When used as fungicides or bactericides, the carboxamides of this invention will be formulated and applied in fungicidal or bactericidal, as the case may be, amounts by conventional 'art methodsto fungi bacteria or hosts which are subject to fungus or bacteria attack, especially vegetative hosts such as plants, plant seeds, paper and the like. They may be combined with inert liquids and solid carriers as powders, solutions or dispersions for such use.

Pesticidal formulations of the carboxamides of this invention may also contain stabilizers, spreading agents, sticking agents, fillers, other compatible pesticides and the like As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim:

1. A method for controlling the growth or organisms which foul aqueous bodies which comprises adding to said aqueous body a biocidal amount of the compound of the formula wherein R is a lower alkyl radical which has zero to three chlorine substituents or cycloalkyl of three to eight carbon atoms, R is hydrogen or lower alkyl with the proviso that R and R may be joined to form a linear alkylene radical of three to five carbon atoms which is bound to the carbonyl andnitrogen to form a ring, X is chlorine and a is 2 or 3.

2. The method of claim 1 wherein X is chlorine and a is 3.

3. The method of claim 1 wherein R is lower alkyl and has 0 to 3 chloro substitucnts.

4. The method of claim 1 wherein R is lower alkyl.

5. The method of claim 1 wherein X is chlorine, a is 3, R is methyl and R is hydrogen 6. The method of claim 1 wherein X is chlorine, a is 3, R and R' are joined to form a linear propylene or amylene radical which is bound to the carbonyl and nitrogen to form a ring.

7. The method of claim 1 wherein the compound is applied at a concentration in the range of about 0.1 to 50 ppm. 

2. The method of claim 1 wherein X is chlorine and a is
 3. 3. The method of claim 1 wherein R is lower alkyl and has 0 to 3 chloro substituents.
 4. The method of claim 1 whereIn R is lower alkyl.
 5. The method of claim 1 wherein X is chlorine, a is 3, R is methyl and R'' is hydrogen.
 6. The method of claim 1 wherein X is chlorine, a is 3, R and R'' are joined to form a linear propylene or amylene radical which is bound to the carbonyl and nitrogen to form a ring.
 7. The method of claim 1 wherein the compound is applied at a concentration in the range of about 0.1 to 50 ppm. 